Azole compounds

ABSTRACT

1. A COMPOUND REPRESENTED BY THE FORMULA,   (=N-C(-AR-)=C-X-)&gt;C-CH=CH-(CYCLOHEX-1,4-YLENE)-C&lt;(=N-N=   C(-PHENYLENE-R2)-Y-)   WHEREIN AR IS UNSUBSTITUTED BENZENE NUCLEUS, UNSUBSTITUTED NAPHTHALENE NUCLEUS OR BENZENE NUCLEUS SUBSTITUTED BY ONE METHYL, METHOXY, ETHOXY, CHLORINE, PHENYL, CARBOETHOXY OR ETHYLSULFONYL GROUP; R2 IS A HYDROGEN OR CHLORINE ATOM OR A LOWER ALKYL OR METHOXY GROUP; X IS OXYGEN, SULFUR, NH GROUP OR N-CH3 GROUP; AND Y IS OXYGEN OR SULFUR.

United States Patent ABSTRACT OF THE DISCLOSURE Azole compounds usefulfor optical brightening agents for synthetic fibers represented by theformula,

wherein Ar is unsubstituted benzene nucleus, unsubstituted naphthalenenucleus or benzene nucleus substituted by one methyl, methoxy, ethoxy,chlorine, phenyl, carboethoxy or ethylsulfonyl group;

R is a hydrogen or chlorine atom or a lower alkyl or methoxy group;

X is oxygen, sulfur, NH group or N-CH group; and

Y is oxygen or sulfur.

CROSS REFERENCE TO RELATED APPLICATIONS This is a continuation-in-partof co-pending application Ser. No. 743,303, filed on July 9, 1968, nowUS. Pat. 3,637,672, granted Jan. 18, 1972.

The present invention relates to azole compounds represented by generalformula (1) depicted below.

wherein Ar is unsubstituted benzene nucleus,, unsubstituted naphthalenenucleus or benzene nucleus substituted by one methyl, methoxy, ethoxy,chlorine, phenyl, carboethoxy or ethylsulfonyl group;

R is a hydrogen or chlorine atom or a lower alkyl or methoxy group;

X is oxygen, sulfur, NH group or N-CH group; and

Y is oxygen or sulfur.

3,840,528 Patented Oct. 8, 1974 is treated with a halogenating agent,such as thionyl chloride, phosphorus trichloride, phosphoruspentachloride, phosphorus oxychloride, thionyl bromide or phosphoruspentabromide, in the usual manner to give the corresponding halogenide,which is then treated with aqueous solution of hydrazine to obtain acompound of the following formula:

N 1ST CCH=CH CONHNH| One mol of the compound of formula (3) is reactedwith 1 mol of a compound represented by the formula in an inert solventin the presence of hydrogen chlorideremoving agent, such as pyridine,and a compound of the formula:

N Ar \C-CH=CHOCONHNHCOO C CH=CH C n0 t .t X (5) In this case, a compoundof formula (5) wherein Y is oxygen is obtained when dehydrating agent isused, while a compound of formula (5) wherein Y is sulfur is obtainedwhen phosphorus pentasulfide is used.

The ring-closing temperature in this method is preferably usually fromto 250 C. In this case, a better yield can be obtained by the use of anorganic solvent, such as toluene, xylene, dichlorobenzene ortrichlorobenzene, in order to avoid unhomogeneous reaction. If desired,the reaction product of formula (5) may be recrystallized from anorganic solvent, such as xylene, dichlorobenzene or cyclohexanone.

2. A carboxylic acid represented by the following formula is treatedwith a halogenating agent to give the corresponding halogenide.

II II NN N Hz to obtain a compound represented by the formula:

R2 Y XH Upon dehydrating and closing the ring of the compound of formula(8), a compound of formula (9) is obtained.

The compound of formula (6) can be produced by the following twomethods:

(A) A compound represented by the formula:

and a hydrazide compound represented by the formula:

are condensed by removing hydrogen chloride, orcinnamonitrile-4-carboxylic acid hydrazide represented by the formulamNnN-coOon=on-on and carboxylic acid chloride represented by the formulaare condensed by removing hydrogen halide, to obtain a compound of thefollowing formula:

{3-0 ONHNHO oOcn=cn-cn (12) Then, the ring of the compound is closed anda compound of the formula:

is obtained. Upon hydrolysis, the compound of formula (6) is produced.

The cinnamonitrile-4-carboxylic acid chloride can be readily obtained byacting chlorinating agent on cinnamonitrile-4-carboxylic acid which canbe produced by the Neerwein reaction from p aminobenzoic acid diazoni-umsalt and acrylonitrile through oc-ChlOl'OhYdlO-cinnamonitrile-4-carboxylic acid.

(B) The compound of formula (6) is produced by the Neerwein reactionbetween diazonium salt, obtained by diazotizing a compound of theformula:

@tr FQ N t t.

The manner in which the azole compounds of the pres-. ent invention areapplied to organic materials, is variable depending upon thecharacteristics of the azole compound used and the type of the organicmaterial to which said azole compound is applied. For dyeing syntheticfibres with an azole type compound which is hard-soluble in water, aknown dyeing method is employed. Namely, an aqueous dispersion of azolecompound is prepared by the use of a suitable surface active agent, e.g.polyoxyethylene ether-type non-ionic surface active agent oralkylbenzene sulfonic acid-type anionic surface active agent, and thefibres are dipped in said dispersion for brightening. In this case, thetreatment temperature is preferably normally in the neighbourhood of 50to 130 C. in accordance with the fibre materials. As for polyester-typesynthetic fibres, the brightening effect may further be improved byadding in the treatment bath a dyeing assistant, such astrichlorobenzene or methyl salicylate. In treating fabrics made ofpolyester-type synthetic fibre or mixture thereof with cotton, it ispreferable to subject the fibres to a hot air treatment according to theso-called pigment padding method. The temperature of 160 to 200 C. ispreferably used for such treatment.

As the other method of treating synthetic fibres, the azole compounds ofthe present invention may be added in the polymers before said polymersare spun into the fibres.

Of the azole compounds of the present invention, those which are solublein water, e.g. those compounds having sul-fonic acid group, are used bythe dyeing method which is adapted for use with acid dyes and directcotton dyes. The compounds of this type are used for natural fibres,such as cotton, wool and silk, and polyamide fibres.

The amount of the azole compounds used in the brightening treatment sofar described is preferably selected normally in the range of 0.01 to0.4% with respect to the amount of the fibre materials.

In use of the azole compounds of the present invention for thebrightening treatment of synthetic resins, it is advantageous, forexample, to mix the azole compound with the polymer before shaping andthen shape the mixture by heat-treating it with a previously heatedroll. The temperature in this case is preferably from to 300 C. and theamount of the azole compound used is preferably normally from 0.005 to2.0%.

Example 1 8.7 g. of a compound represented by the formula,

CHa

was ob ained.

.1 1 Example 19 The process of Example 1 was repeated using 8.3 g. of acompound represented by the formula,

using 5.7 g. of 4-methoxybenzhydrazide instead of 4.7 g. of'benzhydrazide and a compound of the formula,

was obtained.

Analysis: C 72.77%, N 10.35% Calculation: C 72.90%, N 10.63% 413 mp0.000025 g./l. dioxane) This compound was superior to the compound ofExample 3 in the light fastness of an aqueous dispersion thereof andoptically brightening effect. For example, when a Tetoron fabric wastreated with an aqueous dispersion of the respective compound preparedby the aid of a polyoxyethylene ether type surface active agent at 130C. for one hour, 0.16% of the compound of Example 3 based on the weightof the fabric had to be used to obtain the same whiteness as obtainedwith 0.1% of the compound of formula (22). Thus, the compound of formula(22) could provide practically satisfactory optically brighteningeffect.

Example 20 10.3 g. of a compound represented by the formula,

was obtained.

The 13 g. of carboxylic acid amide thus obtained was boiled in 200 cc.of o-dichlorobenzene and 0.7 g. of boric acid for 6 hours while removingthe water generated from the reaction system. After cooling, theprecipitate was filtered, washed with methanol and dried, whereuponabout 10 g. of a compound of the formula,

was obtained. By recrystallizing the compound thus obtained fromo-dichlorobenzene, a light yellow crystal having a melting point of 241to 243 C. was obtained.

12 Analysis: C 75.93%, N 11.10%- Calculation: C 75.97%, N 11.08% F 416 m(0.000025 g./l. dioxane) The carboxylic acid compound used as thestarting material in this Example is prepared in the following manner.

A mixture of 9.6 g. of cinnamonitrile-4-carboxylic acid chloride, 6.8 g.of benzhydrazide and 8 g. of pyridine is heated to C. over a period ofabout 30 minutes in 100 cc. of chlorobenzene with stirring and thereaction was carried out for 2 hours at 100 to C. After cooling, theprecipitate is filtered and dried, and a compound of the formula,

is obtained.

15 g. of the compound thus obtained is heated to 160 C. in 100 cc. ofdichlorobenzene and 6 g. of thionyl chloride and the reaction is carriedout until the mixture becomes completely dissolved. Upon cooling andfiltering the resulting precipitate, a compound of the formula,

is obtained.

10 g. of this compound is reacted with 100 g. of 70% sulfuric acid for 8hours at a temperature not lower than 100 C. and after cooling themixture is poured into icewater and a compound of the formula,

is obtained.

Example 21 A mixture of 10.7 g. of a compound represented by theformula,

200 cc. of o-dichlorobenzene and 5.6 g. of thionyl chloride was heatedto to C. until it stopped generating hydrochloric acid gas and excessthionyl chloride was removed by vacuum distillation along with 50 cc. ofo-dichlorobenzene. 4.9 g. of 4-methyl-2-aminophenol was added to theresidue and the reaction was carried out at 140 to 150 C. for 4 hourswith stirring. 0.5 g. of ptoluene sulfonic acid was added to thecarboxylic acid amide produced, without isolating the latter from thereaction system and the reaction was carried out at the boiling pointwhile removing the water generated by distillation. After 4 hours ofreaction, the mixture was cooled and the precipitate was filtered andwashed with methanol. 12 g. of a compound of the formula,

was obtained.

By recrystallizing the compound from o-dichlorobenzene, a light yellowcrystal having a melting point of 264 to 265 C. was obtained.

Analysis: C 76.29%, N 10.70% Calculation: C 76.32%, N 10.68% F 418 mp(0.000025 g./l. dioxane) The starting material in this Example, that is,carboxylic acid compound, may be prepared in the same manner asdescribed in Example 20, using p-methyl benzhydrazide instead ofbenzhydrazide. Alternatively, it may be prepared in the followingmanner.

25.1 g. of a compound of the formula HmOo o--om 14*.

is diazotized in the usual manner and neutralized with sodium acetate.The resultant solution is poured into a mixture of 10.8 g. of maleicanhydride and 200 cc. of acetone at room temperature, to which is addeda solution of g. of cupric chloride in 20 cc. of water. The mixture isheated to 50 C. after the generation of nitrogen gas has stopped anddiazonium salt has been dissipated. The reaction product is filtered andextracted wtih sodium carbonate, and after adding hydrochloric acid theprecipitate is filtered to otbain a compound of the formula,

Example 22 1 Part of the compound represented by formula (18) wasthoroughly mixed with 99 parts of polyoxyethylene ether-type surfaceactive agent to prepare a sample material. 1 Part of said samplematerial per parts of a Tetoron fabric was thrown into 300 parts ofwater containing 1.5 parts of chlorobenzene-type carrier to obtain adispersion. The Tetoron fabric Was immersed in said dispersion at 100 C.for 60 minutes, and thereafter the Tetoron fabric thus treated waswashed with water and dried. The Tetoron fabric showed a remarkablebrightening effect as compared with untreated fabric.

Similarly, remarkably brightened fabrics were obtained by the use of theazole compounds produced in Examples 2, 3, 11 and 21.

Example 23 A dispersion was prepared by dissolving 0.1 part of thecompound represented by formula (18) in 100 parts of dioxane with heatand pouring the resultant solution into a mixture of 12 parts ofpolyoxyethylene ether-type surface active agent and 3000 parts of water.100 parts each of nylon, vinylon, acetate, polypropylene and cottonfabrics were individually immersed in the dispersion at 95 C. for 45minutes. After washing the individual treated fabrics with water anddrying, fabrics of bluish white color were obtained which were muchbrighter than untreated fabrics. The acetate fabric in particular gave aspecial brightness of purple color.

Similarly, excellent brightening effects were obtained by the use of theazole compounds produced in Examples 7, 14, 17 and 18, instead of thecompound of formula (18).

Example 24 0.01 Part of the compound represented by formula (18), whichwas produced in Example 1, was mixed with 100 parts of polyethylene andthe mixture was kneaded homogeneously on a roll heated to 130 C. andthen pressed into a sheet, whereby a polyethylene sheet having a brightbluish fluorescence was obtained.

Similarly, excellent brightening effects were obtained by using theazole compounds produced in Examples 2, 6 and 9.

Example 25 1 Part of the compound which was produced in Example 21 wasmixed with 9 parts of dioctyl phthalate to prepare a sample material.0.1 Part of the sample material was mixed with 100 parts of polyvinylchloride, 0.2 part wherein Ar is unsubstituted benzene nucleus,unsubstituted naphthalene nucleus or benzene nucleus substituted by onemethyl, methoxy, ethoxy, chlorine, phenyl, carboethoxy or ethylsulfonylgroup;

R is a hydrogen or chlorine atom or a lower alkyl or methoxy group;

X is oxygen, sulfur, NH group or N-CH group; and

Y is oxygen or sulfur.

2. A compound of Claim 1, which is represented by the formula,

Or F-Q N ll 3. A compound of Claim 1, which is represented by theformula,

4. A compound of Claim 1, which is represented by the formula,

5. A compound of Claim 1, which is represented by the formula,

6. A compound of Claim 1, which is represented by the formula,

7. A compound of Claim 1, which is represented by the formula,

8. Compounds of the Formula I 15 16 R1 11. A compound as claimed inClaim 8 which has the /Y\ N R2 formula Q i k ra x R; 5 O-GH-CHQ-C C JCH:

(I) wherein N 12. A com ound as claimed in Claim 8 which has the X and Yrepresent independently oxygen or sulphur, and formula p R and Rrepresent independently hydrogen, an alkyl 10 group having 1 to 4 carbonatoms, the phenyl group or 0 a phenyl group substituted by chlorine,alkyl groups CH CH a g H having 1 to 4 carbon atoms or alkoxy groupshaving 1 to 4 carbon atoms, or alkoxy groups having 1 or 2 N 0 1 carbonatoms, or chlorine, and R represents hydrogen Or chlorin ReferencesCited 9. Compounds according to Claim 3:, wherein R repre- UNITED STATESPATENTS semis hydmgen an alkyl gmuP havmg 1 4 3,635,960 1/1972 DiGiovanoel et a1. 260240D atoms, or the methoxy group, R representshydrogen, an

alkyl group having 1 to 4 carbon atoms, the methoxy group or chlorineand R represents hydrogen or chlorine. JOHN RANDOLPH Pnmary Exammer 10.A compound as claimed in Claim 8 which has the U S C1 X R formula106-176; 11733.5 R, 33.5 T; 252301.2 W, 543;

260-75 T, 77.5 D, 78 SC, 88.7 R, 92.8 A & R, 93.5

N-N QJk /g $55651, 141, 157, 240.9, 240 J, 307 R and G, 469, 471, 1 H\N/ 0

1. A COMPOUND REPRESENTED BY THE FORMULA,